Chemistry

(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Question 12.19:
Describe the method, which can be used to separate two compounds with different
solubilities in a solvent S.
Answer 12.19:
Fractional crystallisation is the method used for separating two compounds with different
solubilities in a solvent S. The process of fractional crystallisation is carried out in four
steps.
(a)

Preparation of the solution: The powdered mixture is taken in a flask and the

solvent is added to it slowly and stirred simultaneously. The solvent is added till the solute
is just dissolved in the solvent. This saturated solution is then heated.
(b)

Filtration of the solution: The hot saturated solution is then filtered through a

filter paper in a China dish.

(c)

Fractional crystallisation: The solution in the China dish is now allowed to cool.

The less soluble compound crystallises first, while the more soluble compound remains in
the solution. After separating these crystals from the mother liquor, the latter is
concentrated once again. The hot solution is allowed to cool and consequently, the crystals
of the more soluble compound are obtained.
(d)

Isolation and drying: These crystals are separated from the mother liquor by

filtration. Finally, the crystals are dried.

Question 12.20:
What is the difference between distillation, distillation under reduced pressure and steam
distillation ?
Answer 12.20:
The differences among distillation, distillation under reduced pressure, and steam
distillation are given in the following table.

21
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Distillation

Distillation
under
reduced pressure

Steam distillation

1.

It is used for the

purification
of
compounds
that
are
associated with nonvolatile impurities or
those liquids, which do
not
decompose
on
boiling. In other words,
distillation is used to
separate volatile liquids
from non-volatile
impurities or a mixture
of those liquids that have
sufficient difference in
boiling points.

This method is used to

purify a liquid that tends
to decompose on boiling.
Under the conditions of
reduced pressure, the
liquid will boil at a low
temperature
than
its
boiling point and will,
therefore, not
decompose.

It is used to purify an
organic compound, which is
steam
volatile
and
immiscible in water. On
passing
steam,
the
compound gets heated up
and
the
steam
gets
condensed to water. After
some time, the mixture of
water and liquid starts to
boil and passes through the
condenser. This condensed
mixture of water and liquid
is then separated by using
a separating funnel.

2.

Mixture of petrol and

kerosene is separated by
this method.

Glycerol is purified by this

method. It boils with
decomposition
at
a
temperature of 593 K. At
a reduced pressure, it
boils at 453 K without
decomposition.

A mixture of water and

aniline is separated by
steam distillation.

Question 12.21:
Discuss the chemistry of Lassaignes test.
Answer 121.21:
Lassaignes test
This test is employed to detect the presence of nitrogen, sulphur, halogens, and
phosphorous in an organic compound. These elements are present in the covalent form in
an organic compound. These are converted into the ionic form by fusing the compound
with sodium metal.

22
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

The cyanide, sulphide, and halide of sodium formed are extracted from the fused mass by
boiling it in distilled water. The extract so obtained is called Lassaignes extract. This
Lassaignes extract is then tested for the presence of nitrogen, sulphur, halogens, and
phosphorous.
(a) Test for nitrogen

Chemistry of the test

In the Lassaignes test for nitrogen in an organic compound, the sodium fusion extract is
boiled with iron (II) sulphate and then acidified with sulphuric acid. In the process, sodium
cyanide first reacts with iron (II) sulphate and forms sodium hexacyanoferrate (II). Then,
on heating with sulphuric acid, some iron (II) gets oxidised to form iron (III)
hexacyanoferrate (II), which is Prussian blue in colour. The chemical equations involved
in the reaction can be represented as

(b) Test for sulphur

Chemistry of the test

In the Lassaignes test for sulphur in an organic compound, the sodium fusion extract is
acidified with acetic acid and then lead acetate is added to it. The precipitation of lead
sulphide, which is black in colour, indicates the presence of sulphur in the compound.

23
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Chemistry of the test

The sodium fusion extract is treated with sodium nitroprusside. Appearance of violet colour
also indicates the presence of sulphur in the compound.

If in an organic compound, both nitrogen and sulphur are present, then instead of NaCN,
formation of NaSCN takes place.
Na + C + N + S NaSCN
This NaSCN (sodium thiocyanate) gives a blood red colour. Prussian colour is not formed
due to the absence of free cyanide ions.

(c) Test for halogens

Chemistry of the test

In the Lassaignes test for halogens in an organic compound, the sodium fusion extract is
acidified with nitric acid and then treated with silver nitrate.

24
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

If nitrogen and sulphur both are present in the organic compound, then the Lassaignes
extract is boiled to expel nitrogen and sulphur, which would otherwise interfere in the test
for halogens.

Question 12.22:
Differentiate between the principle of estimation of nitrogen in an organic compound by
(i) Dumas method and (ii) Kjeldahls method.
Answer 12.22:
In Dumas method, a known quantity of nitrogen containing organic compound is heated
strongly with excess of copper oxide in an atmosphere of carbon dioxide to produce free
nitrogen in addition to carbon dioxide and water. The chemical equation involved in the
process can be represented as

The traces of nitrogen oxides can also be produced in the reaction, which can be reduced
to dinitrogen by passing the gaseous mixture over a heated copper gauge. The dinitrogen
produced is collected over an aqueous solution of potassium hydroxide. The volume of
nitrogen produced is then measured at room temperature and atmospheric pressure.
On the other hand, in Kjeldahls method, a known quantity of nitrogen containing organic
compound is heated with concentrated sulphuric acid. The nitrogen present in the
compound is quantitatively converted into ammonium sulphate. It is then distilled with
excess of sodium hydroxide. The ammonia evolved during this process is passed into a
known volume of H2SO4. The chemical equations involved in the process are

The acid that is left unused is estimated by volumetric analysis (titrating it against a
standard alkali) and the amount of ammonia produced can be determined. Thus, the
percentage of nitrogen in the compound can be estimated. This method cannot be applied
to the compounds, in which nitrogen is present in a ring structure, and also not applicable
to compounds containing nitro and azo groups.

25
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Question 12.23:
Discuss the principle of estimation of halogens, sulphur and phosphorus present in an
organic compound.
Answer 12.23:
Estimation of halogens
Halogens are estimated by the Carius method. In this method, a known quantity of organic
compound is heated with fuming nitric acid in the presence of silver nitrate, contained in
a hard glass tube called the Carius tube, taken in a furnace. Carbon and hydrogen that
are present in the compound are oxidized to form CO 2 and H2O respectively and the
halogen present in the compound is converted to the form of AgX.
This AgX is then filtered, washed, dried, and weighed.
Let the mass of organic compound be m g.
Mass of AgX formed = m1 g
1 mol of Agx contains 1 mol of X.
Therefore,
Mass of halogen in m1 g of AgX

Estimation of Sulphur
In this method, a known quantity of organic compound is heated with either fuming nitric
acid or sodium peroxide in a hard glass tube called the Carius tube. Sulphur, present in
the compound, is oxidized to form sulphuric acid. On addition of excess of barium chloride
to it, the precipitation of barium sulphate takes place. This precipitate is then filtered,
washed, dried, and weighed.
Let the mass of organic compound be m g.
Mass of BaSO4 formed = m1 g
1 mol of BaSO4 = 233 g BaSO4 = 32 g of Sulphur
Therefore, m1 g of BaSO4 contains

Estimation of phosphorus
In this method, a known quantity of organic compound is heated with fuming nitric acid.
Phosphorus, present in the compound, is oxidized to form phosphoric acid. By adding
ammonia and ammonium molybdate to the solution, phosphorus can be precipitated as
ammonium phosphomolybdate.

26
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Phosphorus can also be estimated by precipitating it as MgNH 4PO4 by adding magnesia

mixture, which on ignition yields Mg2P2O7.
Let the mass of organic compound be m g.
Mass of ammonium phosphomolybdate formed = m1 g
Molar mass of ammonium phosphomolybdate = 1877 g

If P is estimated as Mg2P2O7,

Question 12.24:
Explain the principle of paper chromatography.
Answer 12.24:
In paper chromatography, chromatography paper is used. This paper contains water
trapped in it, which acts as the stationary phase. On the base of this chromatography
paper, the solution of the mixture is spotted. The paper strip is then suspended in a
suitable solvent, which acts as the mobile phase. This solvent rises up the chromatography
paper by capillary action and in the procedure, it flows over the spot. The components are
selectively retained on the paper (according to their differing partition in these two
phases). The spots of different components travel with the mobile phase to different
heights. The paper so obtained (shown in the given figure) is known as a chromatogram.

27
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Question 12.25:
Why is nitric acid added to sodium extract before adding silver nitrate for testing halogens?
Answer 12.25:
While testing the Lassaignes extract for the presence of halogens, it is first boiled with
dilute nitric acid. This is done to decompose NaCN to HCN and Na 2S to H2S and to expel
these gases. That is, if any nitrogen and sulphur are present in the form of NaCN and
Na2S, then they are removed. The chemical equations involved in the reaction are
represented as

Question 12.26:
Explain the reason for the fusion of an organic compound with metallic sodium for testing
nitrogen, sulphur and halogens.
Answer 12.26:
Nitrogen, sulphur, and halogens are covalently bonded in organic compounds. For their
detection, they have to be first converted to ionic form. This is done by fusing the organic
compound with sodium metal. This is called Lassaignes test. The chemical equations
involved in the test are

Carbon, nitrogen, sulphur, and halogen come from organic compounds.

Question 12.27:
Name a suitable technique of separation of the components from a mixture of calcium
sulphate and camphor.

28
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Answer 12.27:
The process of sublimation is used to separate a mixture of camphor and calcium sulphate.
In this process, the sublimable compound changes from solid to vapour state without
passing through the liquid state. Camphor is a sublimable compound and calcium sulphate
is a non-sublimable solid. Hence, on heating, camphor will sublime while calcium sulphate
will be left behind.

Question 12.28:
Explain, why an organic liquid vaporises at a temperature below its boiling point in its
steam distillation?
Answer 12.28:
In steam distillation, the organic liquid starts to boil when the sum of vapour pressure due
to the organic liquid (p1) and the vapour pressure due to water (p2) becomes equal to
atmospheric pressure (p), that is, p = p1 + p2
Since p1 < p2, organic liquid will vapourise at a lower temperature than its boiling point.

Question 12.29:
Will CCl4 give white precipitate of AgCl on heating it with silver nitrate? Give reason for
your answer.
Answer 12.29:
CCl4 will not give the white precipitate of AgCl on heating it with silver nitrate. This is
because the chlorine atoms are covalently bonded to carbon in CCl 4. To obtain the
precipitate, it should be present in ionic form and for this, it is necessary to prepare the
Lassaignes extract of CCl4.

Question 12.30:
Why is a solution of potassium hydroxide used to absorb carbon dioxide evolved during
the estimation of carbon present in an organic compound?
Answer 12.30:
Carbon dioxide is acidic in nature and potassium hydroxide is a strong base. Hence, carbon
dioxide reacts with potassium hydroxide to form potassium carbonate and water as

Thus, the mass of the U-tube containing KOH increases. This increase in the mass of Utube gives the mass of CO2 produced. From its mass, the percentage of carbon in the
organic compound can be estimated.

29
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Question 12.31:
Why is it necessary to use acetic acid and not sulphuric acid for acidification of sodium
extract for testing sulphur by lead acetate test?
Answer 12.31:
Although the addition of sulphuric acid will precipitate lead sulphate, the addition of acetic
acid will ensure a complete precipitation of sulphur in the form of lead sulphate due to
common ion effect. Hence, it is necessary to use acetic acid for acidification of sodium
extract for testing sulphur by lead acetate test.
Question 12.32:
An organic compound contains 69% carbon and 4.8% hydrogen, the remainder being
oxygen. Calculate the masses of carbon dioxide and water produced when 0.20 g of this
substance is subjected to complete combustion.
Answer 12.32:
Percentage of carbon in organic compound = 69 %
That is, 100 g of organic compound contains 69 g of carbon.
0.2 g of organic compound will contain

Molecular mass of carbon dioxide, CO2 = 44 g

That is, 12 g of carbon is contained in 44 g of CO2.
Therefore, 0.138 g of carbon will be contained in

= 0.506 g of CO2

Thus, 0.506 g of CO2 will be produced on complete combustion of 0.2 g of organic

compound.
Percentage of hydrogen in organic compound is 4.8.
i.e., 100 g of organic compound contains 4.8 g of hydrogen.
Therefore, 0.2 g of organic compound will contain
It is known that molecular mass of water (H2O) is 18 g.
Thus, 2 g of hydrogen is contained in 18 g of water.
0.0096 g of hydrogen will be contained in

of water

Thus, 0.0864 g of water will be produced on complete combustion of 0.2 g of the organic
compound.

30
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Question 12.33:
A sample of 0.50 g of an organic compound was treated according to Kjeldahls method.
The ammonia evolved was absorbed in 50 mL of 0.5 M H 2SO4. The residual acid required
60 mL of 0.5 M solution of NaOH for neutralisation. Find the percentage composition of
nitrogen in the compound.
Answer 12.33:
Given that, total mass of organic compound = 0.50 g
60 mL of 0.5 M solution of NaOH was required by residual acid for neutralisation.
60 mL of 0.5 M NaOH solution

H2SO4 = 30 mL of 0.5 M H2SO4

Acid consumed in absorption of evolved ammonia is (5030) mL = 20 mL

Again, 20 mL of 0.5 MH2SO4 = 40 mL of 0.5 MNH3
Also, since 1000 mL of 1 MNH3 contains 14 g of nitrogen,
40 mL of 0.5 M NH3 will contain

= 0.28 g of N

Therefore, percentage of nitrogen in 0.50 g of organic compound

= 56 %

Question 12.34:
0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in Carius
estimation. Calculate the percentage of chlorine present in the compound.
Answer 12.34:
Given that,
Mass of organic compound is 0.3780 g.
Mass of AgCl formed = 0.5740 g
1 mol of AgCl contains 1 mol of Cl.
Thus, mass of chlorine in 0.5740 g of AgCl

Percentage of chlorine

31
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Hence, the percentage of chlorine present in the given organic chloro compound is
37.59%.

Question 12.35:
In the estimation of sulphur by Carius method, 0.468 g of an organic sulphur compound
afforded 0.668 g of barium sulphate. Find out the percentage of sulphur in the given
compound.
Answer 12.35:
Total mass of organic compound = 0.468 g [Given]
Mass of barium sulphate formed = 0.668 g [Given]
1 mol of BaSO4 = 233 g of BaSO4 = 32 g of sulphur

Thus, 0.668 g of BaSO4 contains

of sulphur = 0.0917 g of sulphur

Therefore, percentage of sulphur

= 19.59 %

Hence, the percentage of sulphur in the given compound is 19.59 %.

Question 12.36:
In the organic compound CH2=CHCH2CH2CCH, the pair of hydridised orbitals involved
in the formation of: C2 C3 bond is:
(a) sp sp2
(b) sp sp3
(c) sp2 sp3
(d) sp3 sp3
Answer 12.36:

In the given organic compound, the carbon atoms numbered as 1, 2, 3, 4, 5, and 6 are
sp, sp, sp3, sp3, sp2, and sp2 hybridized respectively. Thus, the pair of hybridized orbitals
involved in the formation of C2-C3 bond is sp sp3.

32
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Question 12.37:
In the Lassaignes test for nitrogen in an organic compound, the Prussian blue colour is
obtained due to the formation of:
(a) Na4[Fe(CN)6]
(b) Fe4[Fe(CN)6]3
(c) Fe2[Fe(CN)6]
(d) Fe3[Fe(CN)6]4
Answer 12.37:
In the Lassaignes test for nitrogen in an organic compound, the sodium fusion extract is
boiled with iron (II) sulphate and then acidified with sulphuric acid. In the process, sodium
cyanide first reacts with iron (II) sulphate and forms sodium hexacyanoferrate (II). Then,
on heating with sulphuric acid, some iron (II) gets oxidised to form iron (III)
hexacyanoferrate (II), which is Prussian blue in colour. The chemical equations involved
in the reaction can be represented as

Hence, the Prussian blue colour is due to the formation of Fe4[Fe(CN)6]3.

Question 12.38:
Which of the following carbocation is most stable?
(a)

(b)

(c)

(d)

Answer 12.38:
is

a tertiary carbocation. A tertiary carbocation is the most stable carbocation

due to the electron releasing effect of three methyl groups. An increased + I effect by
three methyl groups stabilizes the positive charge on the carbocation.

33
www.tiwariacademy.com

Chemistry
(www.tiwariacademy.com)

(Chapter 12) (Organic Chemistry Some Basic Principles and Techniques)

(Class XI)

Question 12.39:
The best and latest technique for isolation, purification and separation of organic
compounds is:
(a) Crystallisation
(b) Distillation
(c) Sublimation
(d) Chromatography
Answer 12.39:
Chromatography is the most useful and the latest technique of separation and purification
of organic compounds. It was first used to separate a mixture of coloured substances.

Question 12.40:
The reaction:

is classified as :
(a) electrophilic substitution
(c) elimination

(b) nucleophilic substitution

(d) addition

Answer 12.40:

It is an example of nucleophilic substitution reaction. The hydroxyl group of KOH (OH )

with a lone pair of itself acts as a nucleophile and substitutes iodide ion in CH 3CH2I to form
ethanol.

34
www.tiwariacademy.com